CN102042705B - Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating - Google Patents

Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating Download PDF

Info

Publication number
CN102042705B
CN102042705B CN2010105133529A CN201010513352A CN102042705B CN 102042705 B CN102042705 B CN 102042705B CN 2010105133529 A CN2010105133529 A CN 2010105133529A CN 201010513352 A CN201010513352 A CN 201010513352A CN 102042705 B CN102042705 B CN 102042705B
Authority
CN
China
Prior art keywords
layer
absorber
coating
barrier layer
barrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2010105133529A
Other languages
Chinese (zh)
Other versions
CN102042705A (en
Inventor
托马斯·库克尔科恩
卡梅尔·希尔米
塞巴斯蒂安·德赖尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dario Glass solar Holdings Company
Original Assignee
Schott Solar AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schott Solar AG filed Critical Schott Solar AG
Publication of CN102042705A publication Critical patent/CN102042705A/en
Application granted granted Critical
Publication of CN102042705B publication Critical patent/CN102042705B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S20/00—Solar heat collectors specially adapted for particular uses or environments
    • F24S20/20—Solar heat collectors for receiving concentrated solar energy, e.g. receivers for solar power plants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00—Details of absorbing elements
    • F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
    • F24S70/225—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption for spectrally selective absorption
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00—Details of absorbing elements
    • F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
    • F24S70/25—Coatings made of metallic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00—Details of absorbing elements
    • F24S70/30—Auxiliary coatings, e.g. anti-reflective coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The present invention relates to a radiation-selective absorber coating, especially to a radiation-selective absorber coating for absorber tubes of parabolic trough collectors includes two or more barrier layers; an infrared reflective layer on the barrier layers); at least one cermet absorption layer above the infrared reflective layer and an antireflection layer above the at least one cermet absorption layer. The two or more barrier layers include a first barrier layer of thermally produced oxide and a second barrier layer arranged above it. The second barrier layer is a cermet material including at least one oxide compound and at least one metal. The oxide compound is aluminium oxide, silicon oxide, nickel oxide and/or chromium oxide. The metal is molybdenum, nickel, tungsten and/or vanadium. The invention also includes an absorber tube with the absorber coating on it.

Description

Radiation-selective absorber coating and the absorber tube with radiation-selective absorber coating
Technical field
The present invention relates to the radiation-selective absorber coating according to the preamble of this patent claim 1.The invention still further relates to the absorber tube with this kind of radiation-selective coating, and relate to the method for using this kind of absorber tube operation parabolic trough collector.
Background technology
Absorber coating commonly used is by forming with lower floor: be reflexive in infra-red range and be applied in suprabasil layer; described substrate is metal tube especially; have the cermet coating of high-absorbable and be applied to the protective layer on described cermet coating in the solar spectrum scope, this protective layer is called as anti-reflecting layer and because the high index of refraction of described cermet coating is provided for the surface reflection be reduced on described cermet coating.
Main effort is to realize high as far as possible energy gain.Described energy gain also especially depends on the coefficient of absorptivity α and emissivity ε, always makes every effort to make described absorber coating that high absorptivity (α>95%) and low emissivity (ε<10%) are arranged.
Temperature when in addition, the efficiency of described heat collector is moved by it is determined.Consider this point, wish high as far as possible temperature.Yet in contrast, the durability of the layer system of described absorber coating but along with the rising of operating temperature because aging and/or diffusion process reduce, thereby, for example, the absorbent properties of described cermet coating and be that the reflecting properties of reflexive layer may reduce significantly in infra-red range.
At Michael Lanxner and Zvi Elgat at SPIE the 1272nd volume, Optical Materials Technology for Energy Efficiency and Solar Energy Conversion IX (1990), the 240th to 249 pages, the title of showing is for " for the sunshine of high application of temperature absorber coating optionally, produce (Solar selective absorber coating for high service temperatures by plasma sputtering, produced by plasma sputtering) " in paper, a kind of absorber coating be applied on steel base has been described, this coating comprises by SiO 2anti-reflecting layer, the cermet coating formed and be reflexive molybdenum layer in infra-red range, by Al 2o 3it is between reflexive layer and described substrate that the diffusion impervious layer formed is arranged in described in infra-red range.In such layer system, there is stress, this stress has destruction and the caking that adhesiveness reduces effect or causes described layer system.
DE 102004010689B3 discloses a kind of absorber, and it comprises radiation-selective absorber coating, and this coating has metallic substrates, diffusion impervious layer, metallic reflector, cermet coating and anti-reflecting layer.Described diffusion impervious layer is the oxide skin(coating) that the oxidation component by described metallic substrates forms.
It is reflexive layer that molybdenum is often used in infra-red range.Yet the reflecting properties of molybdenum layer is not best, so wish to use better reflective material.
The operating temperature of known absorber tube is 300-400 ℃ in a vacuum.Because front is listed, main effort is further to improve described operating temperature, but do not affect described cermet coating for example absorbent properties and described in infra-red range, be the reflecting properties of reflexive layer.
Such effort be summarised in C.E.Kennedy's " in to the summary (Review of Mid-to High-Temperature Solar Seletive Absorber Materials) of the selective absorbent material of sunshine of high temperature; Technical Report of the National Renewable Energy Laboratory (technical report of National Renewable Energy Laboratory), publish in July, 2002 " in.It discloses a kind of layer of structure, and this layer structure is by ZrO xn yor ZrC xn yabsorbed layer and be that reflexive Ag or Al layer form in the IR scope, described layer structure is due to Al 2o 3the introducing of diffusion barrier and there is improved aerial heat endurance.What determine in addition is that the heat endurance of described infrared reflecting layer under the pressure reduced can be enhanced by introduce diffusion impervious layer under this layer.For this barrier layer, Cr has been proposed 2o 3, Al 2o 3or SiO 2as described layer material.Hope reaches the stability of argentum reflecting layer and is up to 500 ℃.
Yet this does not have to finish to more durable and improved the pursuit of the layer of absorptivity and emissivity simultaneously.
Therefore, DE 102006056536A1 has described radiation-selective absorber coating, this coating comprises at least two barrier layers, disposed thereon and in the IR scope, be reflexive layer, be arranged in the absorbed layer on described reflecting layer, and comprising the anti-reflecting layer be arranged on described absorbed layer, described radiation-selective absorber coating has high sunshine absorptivity and low thermal emissivity.Although the adhesiveness of this absorber coating is enough, it still needs to improve.
Summary of the invention
Thus, the purpose of this invention is to provide a kind of absorber coating, its each layer has extraordinary adhesiveness, so that described absorber coating is inherent stable.In addition, the purpose of this invention is to provide the absorber tube with this kind of coating and the method that operates the parabolic trough collector that has wherein used this kind of absorber tube.
These purposes are by means of this patent independent claims, reach due to the fact that, the described fact is that the second barrier layer be arranged on described the first barrier layer consists of cermet material, the composition that this cermet material is selected from aluminium oxide, silica, nickel oxide, chromium oxide by least one with at least one be selected from molybdenum, nickel, tungsten, vanadium become to be grouped into.
Preferably, described the second barrier layer consists of cermet material, and this cermet material is comprised of aluminium oxide and molybdenum.Described oxide also can produce lower than stoichiometry ground.In the situation that there are Al in aluminium and molybdenum xo y/ Al/Mo cermet, wherein x can be 1 to 2 value, and y can be 2 to 3 value.
This cermet coating preferably has the thickness of 5nm to 200nm, especially preferably the thickness of 10nm to 50nm.In the situation that thickness is greater than 200nm, the mechanical stress in described layer system becomes too greatly so that the layer on adhesiveness enhancement layer (25) peels off or may peel off by low-down power in tape test.In the situation that thickness is less than 5nm, barrier effect no longer is provided, that is, no longer provide the function of this layer as diffusion impervious layer.
The cermet coating be comprised of aluminium oxide and molybdenum preferably has 20% to 70%, especially preferably 30% to 50% molybdenum activity coefficient.In the situation that activity coefficient is higher than 70%, the too high and barrier effect of the metal ratio in described layer is eliminated.In the situation that activity coefficient is lower than 20%, the adhesiveness in the IR-reflecting layer on barrier layer (24b) goes wrong.
Preferably, the cermet coating as the second barrier layer has constant activity coefficient.
Stop that by bilayer (wherein the first barrier layer consists of thermal oxide, for example contain chromium oxide and/or iron oxide, by for example ferrochrome oxide, being formed) the described layer reflected in the IR scope realized more effectively stoped described base material with respect to the shielding of described substrate, especially iron, from described steel absorber tube, be diffused into, especially be diffused into described is in reflexive layer with being influenced by heat in the IR scope, and has therefore improved the long-term thermal stability of described coating.
Because the second barrier layer is formed by described cermet material, especially by aluminium oxide and molybdenum, formed, the adhesiveness on described barrier layer is compared significantly and is improved with in the prior art those.Improve layer (it preferably exists) owing to arranging that between the first and second barrier layers at least one adheres to, the adhesiveness of whole layer can further be improved significantly.
This adhesiveness enhanced layer packets between described barrier layer is containing molybdenum.Preferably, it consists of molybdenum.This adhesiveness enhancement layer preferably has 2nm to 40nm, especially preferably the thickness of 5nm to 20nm.
Molybdenum does not have optical function in this position in this layer of stacked body.This adhesiveness enhancement layer is inactive.
Preferably, the thickness on first barrier layer on described at least two barrier layers is between 20nm to 100nm.In the situation that thickness is less than 20nm, barrier effect is unsatisfactory, and this depends on the composition of adjacent layer.In the situation that thickness is greater than 100nm, produce thermal stress, this thermal stress may cause layer to separate in some cases.
Can described in the IR scope, be to arrange the 3rd barrier layer between reflexive layer and described absorbed layer, described absorbed layer preferably consists of cermet material, this cermet coating preferably is presented as gradient layer, described the 3rd barrier layer is preferably by Al xo ycompound forms, and wherein x can be 1 or 2 value, and y can be 1,2 or 3 value.It preferably has the thickness of 10nm to 50nm.
The described advantage that is reflexive layer is embedded between barrier layer and formation sandwich associated therewith has in infra-red range is: any material can not from described in infra-red range, be that reflexive layer is diffused into the absorbed layer above it, and absorbent properties that can not damage in this way described absorbed layer.It is hereby ensured the diffusion be suppressed to a great extent in described layer system, especially be diffused into and describedly be in reflexive layer in infra-red range or diffuse out from this layer, and be diffused in described absorbed layer.
In this way, can be under the pressure reduced the operating temperature of 400 ℃, be issued to the high-absorbility of α>95.5% wherein and the low-launch-rate of ε<9% wherein.These property retentions are constant, even still like this after 590 ℃ of lower accelerated ageings 3000 hours.Therefore can improve the efficiency of the heat collector that comprises the absorber tube that is provided with this coating from two aspects: improved selectivity ratios α/ε>0.95/0.1 means higher radiant energy income simultaneously, can realize more effectively converting to electric energy with the operating temperature improved, the corresponding parabolic trough collector that just can guarantee to comprise the absorber tube applied in this way the service life that coating only in this way is long moves economically.
Specifically, the heat-resisting quantity of described absorber coating allows to use cheap heat-carrying agent.The high thermal stability of described absorber coating allows the operating temperature of described absorber tube>450 ℃ until 550 ℃.
Advantageously, can use heat-carrying agent, the especially water of boiling point<110 ℃.Under high like this operating temperature, produce water vapour, it can directly be introduced in steam turbine plant.No longer need by heat from before applied oil be passed to the additional heat exchanger of water, therefore according to this viewpoint, the parabolic trough collector that comprises the absorber tube with absorber coating according to the present invention can be very economical move feasiblely.
Another advantage is: described heat transport fluid can be lowered through the flowing velocity of described absorber tube, and this is because higher operating temperature allows, and for the not infringement of described absorber tube coating.Can save the energy of the pump for operating parabolic trough collector in this way.
Described be that reflexive layer is embedded between barrier layer and has following additional advantage in infra-red range: for described layer, can adopt for example silver, copper, platinum or golden material, although they more easily spread, but there is following decisive advantage than molybdenum: i.e. their reflections significantly better in infra-red range, so that can reach emissivity ε<10%.
Preferably, described is that reflexive layer comprises gold in the IR scope, silver, platinum or copper or, by gold, silver, platinum or copper form.
Described is the thickness 50nm to 250nm preferably of reflexive layer in infra-red range, and this depends on described material.In this thickness range, if use especially copper or silver, the layer thickness of 100nm to 150nm is preferred.Specifically, when using silver, can also preferred 60nm to 150nm, the preferably layer thickness of 80nm to 150nm.110nm ± 10nm is particularly preferred.In other cases, 50nm to 100nm, especially 50 to 80nm layer thickness are also suitable.
For described in infra-red range, be reflexive layer, can adopt these little bed thickness, because material gold, silver, platinum and copper all have significantly higher reflectivity, and owing to being stacked between two barrier layers, it can not diffuse in other layer, can not affect due to the diffusion of other interference element their favourable performances in other words.
The higher cost of noble metal Au, Ag and Pt can by for described in infra-red range, be that the known bed thickness of reflexive layer is compared obviously less bed thickness and compensated, in some cases or even overcompensation.
The thickness of described absorbed layer is 60nm to 180nm preferably, especially preferably 80nm to 150nm.Cermet coating that described absorbed layer preferably is comprised of aluminium oxide and molybdenum or that formed by zirconia and molybdenum.Also can provide a plurality of has the different absorbed layers (metal ratio that especially has minimizing) that form or also can provide the absorbed layer gradually changed to replace uniform absorbed layer.This cermet coating is gradient layer preferably, this gradient layer be interpreted as referring in described layer metal ratio increase continuously or reduce continuously (and progressively increase in practice or reduce) layer.
The layer thickness that is positioned at the anti-reflecting layer on described absorbed layer is preferably 60 to 120nm, preferably 70nm to 110nm.This layer preferably consists of silica or aluminium oxide.
Absorber tube, absorber tube in particular for parabolic trough collector, comprise steel pipe, arranged radiation-selective absorber coating on this steel pipe outside, it is reflexive layer that this coating comprises at least one in infra-red range, comprise at least one and be arranged in the absorbed layer (it especially is comprised of cermet material) on described reflecting layer, and comprise the anti-reflecting layer be applied on described absorbed layer, described be that reflexive layer is arranged at least two barrier layers in infra-red range, and first barrier layer on described at least two barrier layers consists of thermogenetic oxide, it is characterized in that, second barrier layer on described at least two barrier layers consists of cermet material, this cermet material is comprised of aluminium oxide and molybdenum.
In described absorber coating is summarised as to preferred embodiment, described absorber tube preferably has radiation-selective absorber coating.
Preferably, the cermet coating be comprised of aluminium oxide and molybdenum has 20% to 70%, preferably 30% to 50% molybdenum activity coefficient.
Preferably, comprise molybdenum, the adhesiveness enhancement layer preferably consisted of molybdenum is arranged on described absorber tube between described the first and second barrier layers.
Employing is according to absorber coating of the present invention with according to absorber tube of the present invention, can be operated the method for parabolic trough collector, described parabolic trough collector has the absorber tube that heat-carrying agent is flowed through, wherein use the absorber tube with radiation-selective absorber coating, described radiation-selective absorber coating has the layer that at least one is reflection in infra-red range, at least one is arranged in the absorbed layer on this reflecting layer, especially the absorbed layer formed by cermet material, with the anti-reflecting layer be arranged on described absorbed layer, at least two barrier layers are arranged between described absorber tube and described reflecting layer, the first barrier layer in the face of described absorber tube in described barrier layer consists of thermogenetic oxide, and the second barrier layer be arranged on described the first barrier layer consists of cermet material, this cermet material is comprised of aluminium oxide and molybdenum.
Thermal liquid, especially water with boiling point<110 ℃ can be as by the thermal liquids of described absorber tube.Yet, also can use and there is more high boiling thermal liquid.
According to another embodiment, for the method that operates parabolic trough collector, stipulated: the operating temperature of described absorber tube should be set as 450 ℃ to 550 ℃, especially is set as 480 ℃ to 520 ℃.
For the method for moving parabolic trough collector, preferably with absorber tube, operate, described absorber tube has radiation-selective absorber coating in described absorber coating is summarised as to preferred embodiment.
The accompanying drawing explanation
Below illustrate in greater detail with reference to the accompanying drawings exemplary embodiment of the present invention.
In the accompanying drawings:
Fig. 1 shows parabolic trough collector, and
Fig. 2 shows the section through absorber tube according to an embodiment of the invention.
Fig. 1 has shown parabolic trough collector 10, and it comprises the elongated paraboloid 11 with parabola profile.Paraboloid 11 is fixed by supporting structure 12.Along the focal line of paraboloid 11, extending absorber tube 13, it is fixed on support 14, and this support is connected with described parabolic trough collector.Paraboloid 11 and support 14 and absorber tube 13 formation ，Gai unit, unit rotate also the therefore position of single shaft ground sun-tracing S around the axis of absorber tube 13.The parallel solar radiation polished object face reflector 11 that sun S injects focuses on absorber tube 13.Heat-carrying agent, especially water flow through absorber tube 13, and this absorber tube is heated by the sunshine that is absorbed.The port of export at described acceptor pipe can take out described heat transfer medium and it is flowed to energy consumer or energy converter.
Fig. 2 has schematically shown the section through absorber tube 13.Absorber tube 13 has the steel pipe 1 that heat-carrying agent 2 flows through, and this steel pipe has formed the substrate that is applied to the absorber coating 20 on pipe 1 outside.The bed thickness of each layer of absorber coating 20 is exaggerated and describes for simple declaration, and has approximately equalised thickness.
Absorber coating 20 from outwards have by means of thermal oxide and be applied to the first barrier layer formed by the ferrochrome oxide or the diffusion impervious layer 24a on steel pipe 1.Applied the adhesiveness enhancement layer formed by molybdenum thereon.Be embedded in infra-red range the layer 21 that is reflexive and is formed by gold, silver, platinum or copper thereon, between the second barrier layer 24b formed by cermet material (this cermet material is comprised of aluminium oxide and molybdenum) and the 3rd barrier layer 24c.Applied cermet coating 22 on the 3rd barrier layer 24c, and this layered system outwards stops with anti-reflecting layer 23.
Apply the absorber tube according to the embodiment of Fig. 2 by following method.
By steel pipe 1, preferably stainless steel tube polishing then cleaning.In polishing process, surface roughness preferably reaches Ra<0.2 μ m.Make subsequently described stainless steel tube in temperature for>400 ℃ of lower thermal oxide half an hour to 2 hour, especially about 1 hour of 500 ℃ of lower thermal oxides.In this process, form 15nm to 50nm, be preferably the oxide skin(coating) that 30nm ± 10nm is thick, as the first barrier layer 24a.
Subsequently, described steel pipe is encased in Vacuum coating device and this equipment is vacuumized.Be less than 5 * 10 -4millibar, be preferably 1 * 10 -4after the pressure of millibar, by means of physical vapor deposition (PVD), especially by means of cathodic sputtering, apply layer subsequently.Make described steel pipe be guided through in rotary manner sputtering source for this reason, namely by by described coated substance, Al for example, the target that Ag and Mo form.
In the first deposition step, by described steel pipe being guided through in rotary manner to described target, apply the adhesiveness enhancement layer formed by Mo.The thickness of described layer is 5nm to 20nm.
In the second deposition step, be guided through between the source be arranged opposite to each other with rotation mode by making described pipe, and apply the second barrier layer 24b with the form of multilayer.Set in this case 10 -2millibar is to 10 -3millibar, preferably 4 * 10 -3millibar is to 7 * 10 -3the air chamber pressure (argon gas) of millibar.Oxygen is supplied with to the aluminium target to produce aluminium oxide.The preferred layer thickness on this second barrier layer is 10nm to 50nm, and very especially preferred 30nm ± 10nm.Described molybdenum activity coefficient has 20% to 70% value in layer thickness in constant mode.
In the 3rd deposition step subsequently, being applied in infra-red range is reflexive layer 21, and described applying is by making gold, silver, platinum or copper, preferably silver, with 60nm to 150nm, the thickness of especially preferred 110nm ± 10nm is deposited on the second barrier layer 24b above to carry out.
Apply another SiO in the 4th deposition step x-or Al xo ythe 3rd barrier layer 24c of layer form, described apply be by make silicon or sputtered aluminum and in the situation that input oxygen deposit reactively and carry out.The preferred bed thickness on this 3rd barrier layer is 50nm, particularly preferably 10nm ± 5nm at the most.Yet this barrier layer also can be saved fully, because have been found that: be applicable to if be applied to the composition of the absorbed layer 22 on reflecting layer 21, just needn't stop diffusion by an additional barrier layer.
In the 5th deposition step, by aluminium and molybdenum are applied to described absorbed layer from a common crucible or by two evaporate/sputters of the target separated simultaneously, at this cermet coating 22.In this case, oxygen is incorporated in the sputter area of aluminium target, in order to go back deposition of aluminium oxide except molybdenum simultaneously.
In this case, in the 5th deposition step, by the described running parameter of suitable selection (amount of sputter rate and oxygen), can differently set and change and form in layer deposition process.Especially when the target used separately, can in absorbed layer 22, with respect to depositing of aluminium oxide part, change the deposition that the molybdenum part is set on ground.In other words, the molybdenum ratio of absorbed layer 22 is set to gradient, and in this case, it preferably reduces in applying absorbed layer 22 processes.Therefore described cermet coating is comprised of a plurality of thin independent stratums, and they consist of aluminium oxide and molybdenum with alternate sequence, and the thickness of described molybdenum layer reduces along outward direction.Inside, the molybdenum ratio is preferably 25% to 70% (volume), 40 ± 15% (volumes) particularly preferably, and outwards be reduced to 10% to 30% (volume), especially preferably 20 ± 10% (volumes).
With respect to the aluminum portions of deposition, the interpolation of oxygen is preferably undertaken by not enough Chemical Calculation ground, so that retains unoxidized aluminum portions in absorbed layer 22.This is then applicable as oxidation-reduction potential or oxygen getter, so that does not have molybdenum oxide to form.Unoxidized aluminum portions in absorbed layer 22 is preferably lower than 10% (volume) for total composition of absorbed layer, especially preferably between 0 and 5% (volume).Described unoxidized aluminum portions equally also can change by changing operating parameter within absorbed layer, the evaporation rate that described operating parameter is oxygen and amount.
Generally, preferably applying thickness is 60nm to 180nm, especially preferably 80nm to 150nm, the particularly preferably absorbed layer 22 of 120 ± 30nm.
In the 6th deposition step, by by means of physical vapor deposition silicon in oxygen, depositing SiO 2layer, apply with SiO 2the anti-reflecting layer 23 of layer form.So the preferred thickness of the anti-reflecting layer 23 of deposition is 70nm to 110nm, especially preferably 90 ± 10nm.
The absorber tube of producing has in this way been heated 250 hours in vacuum heater under 550 ℃.Pressure in vacuum chamber is less than 1 * 10 between this period of heating -4millibar.After 250 hours, heating is closed.After sample being cooled to below 100 ℃, make described vacuum chamber ventilate and remove sample.Then sample has been carried out to spectrum analysis, in this process, can determine that the whole sunshine absorptivity of the direct solar spectrum of AM 1.5 and wave-length coverage 350-2500nm is 95.5% ± 0.5%.For the base reservoir temperature of 400 ℃, thermal emissivity is measured as 8% ± 2%.
Except the sample applied according to said method, also be coated in the sample that there is no the second barrier layer under metallic reflector (21) and there is pure zirconia silicon layer or pure Al 2o 3layer substitutes the sample according to cermet coating of the present invention as the second barrier layer.After coating, the adhesion strength test (" adhesive tape test ") in the enterprising enforcement of described coating with the binder film band.In the situation that there is no the sample on the second barrier layer and in the situation that there is the sample of pure zirconia silicon layer as the second barrier layer, confirm the separation of described coating when the value of shutting down of<10N.There is pure Al 2o 3in the situation of sample of layer, the adhesion up to about 20N can be detected, but in 24 hours because cracking appears in the high inherent strain in described coating.In the situation that the sample produced according to said method can carry out not having up to the shutting down test of 40N layer to separate.Under 590 ℃, make sample repeat these experiments after aging 10 hours and there is identical result.
Therefore not only there is other performance needed for example high sunshine absorptivity and low thermal emissivity according to absorber coatings of the present invention, and there is each layer good adhesion to each other.
Especially the adhesiveness on barrier layer compared with prior art is significantly improved.
Reference numerals list
1 steel pipe
2 thermal liquids
10 parabolic trough collectors
11 paraboloids
12 supporting structures
13 absorber tubes
14 supports
20 radiation-selective absorber coatings
21 is reflexive layer in infra-red range
22 absorbed layers
23 anti-reflecting layers
24a the first barrier layer
24b the second barrier layer
24c the 3rd barrier layer
25 adhesiveness enhancement layers

Claims (18)

1. radiation-selective absorber coating (20), it is reflexive layer (21) that this coating is included in infra-red range, at least one is arranged in described is absorbed layer (22) on reflexive layer (21) in infra-red range, and comprise the anti-reflecting layer (23) be arranged on absorbed layer (22), wherein said be that reflexive layer (21) is arranged at least two barrier layers in infra-red range, and the first barrier layer (24a) in described at least two barrier layers consists of thermogenetic oxide, it is characterized in that, the second barrier layer (24b) be arranged on described the first barrier layer in described at least two barrier layers consists of cermet material, this cermet material is selected from aluminium oxide by least one, silica, nickel oxide, the composition of chromium oxide is selected from molybdenum with at least one, nickel, tungsten, the one-tenth of vanadium is grouped into.
2. according to the absorber coating (20) of claim 1, it is characterized in that, described absorber coating (20) is the radiation-selective absorber coating for the absorber tube (13) of parabolic trough collector (10).
3. according to the absorber coating (20) of claim 1, it is characterized in that, the second barrier layer (24b) consists of cermet material, and this cermet material is comprised of aluminium oxide and molybdenum.
4. according to the absorber coating (20) of claim 3, it is characterized in that, the second barrier layer (24b) has 20% to 70% molybdenum activity coefficient.
5. according to the absorber coating (20) of any one in claim 1 to 4, it is characterized in that, arrange at least one adhesiveness enhancement layer (25) between the first barrier layer (24a) and the second barrier layer (24b).
6. according to the absorber coating (20) of claim 5, it is characterized in that, described adhesiveness enhancement layer (25) is comprised of molybdenum.
7. according to the absorber coating (20) of any one in claim 1 to 4, it is characterized in that, the thickness of the second barrier layer (24b) is 5nm to 200nm.
8. according to the absorber coating (20) of any one in claim 1 to 4, it is characterized in that, absorbed layer (22) consists of cermet material.
9. according to the absorber coating (20) of any one in claim 1 to 4, it is characterized in that, be that reflexive layer (21) comprises gold, silver, platinum or copper in infra-red range, or formed by gold, silver, platinum or copper.
10. according to the absorber coating (20) of any one in claim 1 to 4, it is characterized in that, be that the thickness of reflexive layer (21) is 50nm to 150nm in infra-red range.
11. the absorber coating (20) according to any one in claim 1 to 4 is characterized in that the first barrier layer (24a) is the ferrochrome oxide skin(coating).
12. the absorber coating (20) according to any one in claim 1 to 4 is characterized in that absorbed layer (22) has the thickness of 60nm to 140nm.
13. absorber tube (13), this absorber tube comprises steel pipe (1), applied radiation-selective absorber coating (20) on this steel pipe outside, it is reflexive layer (21) that this coating has at least one in infra-red range, at least one is arranged in described is absorbed layer (22) on reflexive layer (21) in infra-red range, with the anti-reflecting layer (23) be arranged on absorbed layer (22), at least two barrier layers (24) are arranged in steel pipe (1) and are between reflexive layer (21) in infra-red range, the first barrier layer (24a) be applied in described barrier layer on steel pipe (1) is comprised of thermogenetic oxide, the second barrier layer (24b) be arranged on the first barrier layer (24a) consists of cermet material, this cermet material is selected from aluminium oxide by least one, silica, nickel oxide, the composition of chromium oxide is selected from molybdenum with at least one, nickel, tungsten, the one-tenth of vanadium is grouped into.
14. the absorber tube (13) according to claim 13 is characterized in that described absorber tube (13) is the absorber tube for parabolic trough collector.
15. the absorber tube (13) according to claim 13 is characterized in that the second barrier layer (24b) consists of cermet material, this cermet material is comprised of aluminium oxide and molybdenum.
16. the absorber tube (13) according to claim 13 to any one in 15, is characterized in that, arranges at least one adhesiveness enhancement layer (25) between the first barrier layer (24a) and the second barrier layer (24b).
17. the absorber tube (13) according to claim 16 is characterized in that described adhesiveness enhancement layer (25) is comprised of molybdenum.
18. the absorber tube (13) according to claim 15 is characterized in that the second barrier layer (24b) has 20% to 70% molybdenum activity coefficient.
CN2010105133529A 2009-10-15 2010-10-15 Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating Active CN102042705B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009049471A DE102009049471B3 (en) 2009-10-15 2009-10-15 Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating
DE102009049471.5 2009-10-15

Publications (2)

Publication Number Publication Date
CN102042705A CN102042705A (en) 2011-05-04
CN102042705B true CN102042705B (en) 2013-06-19

Family

ID=43481154

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010105133529A Active CN102042705B (en) 2009-10-15 2010-10-15 Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating

Country Status (8)

Country Link
US (1) US8555871B2 (en)
EP (1) EP2312234B1 (en)
CN (1) CN102042705B (en)
CY (1) CY1118631T1 (en)
DE (1) DE102009049471B3 (en)
ES (1) ES2614156T3 (en)
IL (1) IL208302A (en)
PT (1) PT2312234T (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008057868B4 (en) * 2008-11-18 2015-01-22 Deutsches Zentrum für Luft- und Raumfahrt e.V. Parabolic trough collector
JP5743487B2 (en) * 2010-10-25 2015-07-01 イビデン株式会社 Heat collector tube, collector, and concentrating solar power generation system
TW201351674A (en) * 2012-06-13 2013-12-16 Ind Tech Res Inst Solar power system and solar energy collection device thereof
EP2677249A1 (en) * 2012-06-22 2013-12-25 Siemens Concentrated Solar Power Ltd. Heat receiver tube with a diffusion barrier layer
CN102721209A (en) * 2012-06-29 2012-10-10 苏州嘉言能源设备有限公司 Non-vacuum groove type barrier coating for solar power generation
TWI485894B (en) * 2012-11-23 2015-05-21 Ind Tech Res Inst Thermoelectric conversion device and selective absorber film
ITVI20130006A1 (en) * 2013-01-16 2014-07-17 Fond Bruno Kessler MULTI-LAYER COATING WITH HIGH ABSORPTION OF SOLAR ENERGY AND LOW THERMAL EMISSION, A RELATED CERMET COMPOSITE, ITS USE AND PROCEDURES FOR THEIR PRODUCTION
US20140261390A1 (en) * 2013-03-13 2014-09-18 Brightsource Industries (Israel) Ltd. High temperature radiation-selective coating and related apparatus
JP6193688B2 (en) * 2013-05-07 2017-09-06 株式会社豊田自動織機 Solar-heat converter and solar power generator
CN103267379B (en) * 2013-05-27 2015-01-14 欧阳俊 Full nitride weather-resisting photo-thermal coating and preparing method thereof
TWI542843B (en) * 2013-12-10 2016-07-21 財團法人工業技術研究院 Selective absorber film and radiation heat recovery generator
WO2016205672A1 (en) * 2015-06-19 2016-12-22 University Of Houston System Selective solar absorbers with tuned oxygen deficiency and methods of fabrication thereof
DE102015114095A1 (en) * 2015-08-25 2017-03-02 Alanod Gmbh & Co. Kg Reflecting composite material with an aluminum support and with a silver reflection layer
DE102016100355A1 (en) * 2016-01-11 2017-07-13 Institut Für Solarenergieforschung Gmbh Multi-layer material sequence for energy production from sunlight, their production and their use
ES2877451T3 (en) * 2016-01-29 2021-11-16 Toyota Jidoshokki Kk Solar heat collector tube and production procedure of the same
EP3222931A1 (en) * 2016-03-22 2017-09-27 POLYCSP ApS Solar selective coating
CN108468016A (en) * 2018-03-15 2018-08-31 兰州交大常州研究院有限公司 Cermet complex spectrum coating for selective absorption and preparation method thereof
MX2020010771A (en) * 2018-04-13 2020-12-09 Solar Avances Y Sist De Energia S L Tracking device.
IT202000018676A1 (en) * 2020-07-30 2022-01-30 Agenzia Naz Per Le Nuove Tecnologie Lenergia E Lo Sviluppo Economico Sostenibile Enea SPECTRALLY SELECTIVE SOLAR ABSORBENT COATING

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1584445A (en) * 2003-08-20 2005-02-23 中国科学院广州能源研究所 NiCrOxNy solar spectrum selective absorbing thin-membrane and preparing method thereof
CN1670446A (en) * 2004-02-27 2005-09-21 肖特股份有限公司 Absorber containing selective radiation absorption coating and preparation method thereof
CN101134855A (en) * 2007-10-16 2008-03-05 河北工业大学 Infrared radiation paint
CN101294749A (en) * 2007-04-24 2008-10-29 梁美意 Heat-collecting tube with solar energy selective absorption coating and manufacturing method thereof

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4202006A (en) * 1978-02-15 1980-05-06 Rca Corporation Semiconductor integrated circuit device
DE2811393A1 (en) 1978-03-16 1979-09-27 Reynolds Metals Co Electroplating aluminium with thin solar energy absorbing coatings - comprising molybdenum and molybdenum oxide(s)
US4446199A (en) * 1982-07-30 1984-05-01 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Overlay metallic-cermet alloy coating systems
DE3374899D1 (en) * 1982-10-08 1988-01-21 Univ Sydney Solar selective surface coating
IN185567B (en) * 1991-07-19 2001-03-03 Univ Sydney
FR2728559B1 (en) * 1994-12-23 1997-01-31 Saint Gobain Vitrage GLASS SUBSTRATES COATED WITH A STACK OF THIN LAYERS WITH INFRARED REFLECTION PROPERTIES AND / OR IN THE FIELD OF SOLAR RADIATION
FR2734811B1 (en) * 1995-06-01 1997-07-04 Saint Gobain Vitrage TRANSPARENT SUBSTRATES COATED WITH A STACK OF THIN LAYERS WITH REFLECTIVE PROPERTIES IN THE INFRARED AND / OR IN THE FIELD OF SOLAR RADIATION
FR2757151B1 (en) * 1996-12-12 1999-01-08 Saint Gobain Vitrage GLAZING COMPRISING A SUBSTRATE PROVIDED WITH A STACK OF THIN FILMS FOR SUN PROTECTION AND / OR THERMAL INSULATION
EP0918044A1 (en) 1997-11-19 1999-05-26 Glaverbel Solar control glazing
US6632542B1 (en) * 2000-05-11 2003-10-14 Sandia Corporation Solar selective absorption coatings
DE20021644U1 (en) * 2000-12-20 2002-05-02 ALANOD Aluminium-Veredlung GmbH & Co.KG, 58256 Ennepetal Solar collector element
DE10150738C1 (en) 2001-10-13 2003-05-22 Schott Glas Process for producing a glass tube with a radiation-absorbing, aging-resistant coating and its use
DE10231467B4 (en) * 2002-07-08 2004-05-27 Schott Glas Absorber tube for solar thermal applications
CN100343413C (en) 2002-12-30 2007-10-17 北京欧科能太阳能技术有限公司 Solar energy selective absorptive coating and its preparing method
AU2003903853A0 (en) 2003-07-25 2003-08-07 Antoine Bittar Barriers, materials and processes for solar selective surfaces
DE10351474B3 (en) * 2003-11-04 2005-05-12 Deutsches Zentrum für Luft- und Raumfahrt e.V. parabolic trough collector
EP1714333A2 (en) * 2004-01-06 2006-10-25 Cymbet Corporation Layered barrier structure having one or more definable layers and method
FR2869898B1 (en) * 2004-05-05 2007-03-30 Saint Gobain SUBSTRATE PROVIDED WITH A STACK WITH THERMAL PROPERTIES
DE102004038233A1 (en) * 2004-08-05 2006-03-16 Schott Ag solar absorber
US7732229B2 (en) * 2004-09-18 2010-06-08 Nanosolar, Inc. Formation of solar cells with conductive barrier layers and foil substrates
US7695805B2 (en) * 2004-11-30 2010-04-13 Tdk Corporation Transparent conductor
DE102004060982B3 (en) 2004-12-17 2006-11-23 Alanod Aluminium-Veredlung Gmbh & Co. Kg Covering for solar absorber has a functional layer including at least one layer containing silicium as its main cationic component
US20060141265A1 (en) 2004-12-28 2006-06-29 Russo David A Solar control coated glass composition with reduced haze
PL1888476T3 (en) 2005-05-11 2019-06-28 Agc Glass Europe Multilayer stack for solar protection
NZ564166A (en) * 2005-05-12 2011-05-27 Agc Flat Glass Na Inc Low emissivity coating with low solar heat gain coefficient, enhanced chemical and mechanical properties and method of making the same
DE102005057277B4 (en) 2005-11-25 2010-08-12 Schott Ag absorber tube
DE202006009369U1 (en) 2006-06-13 2007-10-18 Alanod Aluminium-Veredlung Gmbh & Co. Kg Weatherproof composite material
DE102006056536B9 (en) * 2006-11-27 2008-06-05 Schott Ag Radiation-selective absorber coating, absorber tube and method for its production
WO2009051595A1 (en) * 2007-10-18 2009-04-23 Midwest Research Institue High temperature solar selective coatings
DE102008010199A1 (en) 2008-02-20 2009-08-27 Schott Ag Radiation-selective absorber coating, absorber tube and method for its production
DE102009022059A1 (en) * 2009-05-20 2010-11-25 Schott Solar Ag Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating
US8652870B2 (en) * 2011-10-27 2014-02-18 Intermolecular, Inc. Method of fabricating CIGS by selenization at high temperature

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1584445A (en) * 2003-08-20 2005-02-23 中国科学院广州能源研究所 NiCrOxNy solar spectrum selective absorbing thin-membrane and preparing method thereof
CN1670446A (en) * 2004-02-27 2005-09-21 肖特股份有限公司 Absorber containing selective radiation absorption coating and preparation method thereof
CN101294749A (en) * 2007-04-24 2008-10-29 梁美意 Heat-collecting tube with solar energy selective absorption coating and manufacturing method thereof
CN101134855A (en) * 2007-10-16 2008-03-05 河北工业大学 Infrared radiation paint

Also Published As

Publication number Publication date
PT2312234T (en) 2017-01-09
CY1118631T1 (en) 2017-07-12
ES2614156T3 (en) 2017-05-29
EP2312234A2 (en) 2011-04-20
CN102042705A (en) 2011-05-04
IL208302A (en) 2015-08-31
EP2312234A3 (en) 2014-04-23
US20110088687A1 (en) 2011-04-21
US8555871B2 (en) 2013-10-15
EP2312234B1 (en) 2016-11-16
IL208302A0 (en) 2011-02-28
DE102009049471B3 (en) 2011-04-07

Similar Documents

Publication Publication Date Title
CN102042705B (en) Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating
CN101191677B (en) Radiation selective absorber coating, absorber pipe, and method of making same
CN101514853B (en) Radiation-selective absorber coating, absorber tube and method for its manufacture
CN101900446B (en) Radiation-selective absorber coating and absorber tube with radiation-selective absorber coating
ES2608031T3 (en) Solar selective absorbent coating and manufacturing method
CN101408354B (en) Solar selective absorption coating and preparing method thereof
CN104048432A (en) High temperature radiation-selective coating and related apparatus
CN101876490B (en) Solar energy medium-high temperature selective heat absorbing coating
US20050189525A1 (en) Radiation-selective absorber coating with an adherent oxide layer and method of making same
EP2245208A2 (en) Method for producing a cermet-based spectrally selective coating and material thus obtained
CN103029374A (en) Medium-high temperature solar photothermal selective absorbing coating
JP2015111011A (en) Light selective absorption film, heat collection pipe, and solar heat power generation system
CN203274309U (en) Solar energy absorbing coating and arrangement of same on substrate
EP2995882B1 (en) Solar-thermal conversion member, solar-thermal conversion stack, solar-thermal conversion device, and solar-thermal power generating device
CN104279779A (en) Metal nitride solar spectrum selective absorption coating
CN104279780B (en) A kind of transition metal nitride heat absorbing coating
CN106322799A (en) Solar spectral selective absorbing coating used in medium and low vacuum environment

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20170204

Address after: Spain Asturias

Patentee after: Dario Glass solar Holdings Company

Address before: Germany Mainz

Patentee before: Schott Solar Ag